2-(halomethyl)-alpha-(methoxyimino) benzeneacetic acid methyl ester

ABSTRACT

Compounds of the formula (I): ##STR1## and stereoisomers thereof, wherein X is halogen, alkyl, cycloalkyl, aralkyl, aryloxyalkyl, alkenyl, alkynyl, aryl, amino, arylazo, heteroarylalkyl, heteroaryloxyalkyl, acylamino nitro, nitrile, trifluoromethyl, --OR 1 , SR 1 , --CO 2  R 2 , --CONR 3  R 4 , --COR 5 , --CR 6  ═NR 7 , --N═CR8R 9 , --SOR 10  or --SO 2  R 11  ; W, Y and Z, which may be the same or different, are any of the atoms or groups listed for X above and, in addition, may be hydrogen atoms; or any two of the groups W, X, Y and Z, in adjacent positions on the phenyl ring, optionally join to form a fused ring, either aromatic or aliphatic, optionally containing one or more heteroatoms; R 1  is alkyl, or cycloalkyl optionally containing a heteroatom in the cycloalkyl ring, alkenyl, acyl, aryl, heteroaryl, aralkyl or heteroarylalkyl; R 2 , R 3 , R 4 , R 5 , R 6 , R 8 , R 9 , R 10  and R 11 , which may be the same or different, are hydrogen or alkyl, cycloalkyl, cycloalkylalkyl, alkenyl, aralkyl, aryl or heteroaryl; and R 7  is aryl, the alkyl, cycloalkyl, aralkyl, aryloxyalkyl, alkenyl, alkynyl, aryl, amino, arylazo, heteroarylalkyl, heteroaryloxyalkyl, acylamino, acyl, and heteroaryl being optionally substituted. The compounds are useful as fungicides and as plant growth regulators.

This is a division of application Ser. No. 382,058, filed Jul. 14, 1989,now abandoned, which is a continuation of Ser. No. 069,702, filed Jun.30, 1987, now abandoned.

This invention relates to derivatives of acrylic acid useful inagriculture (especially as fungicides but also as plant growthregulators) to processes for preparing them, to agricultural (especiallyfungicidal) compositions containing them, and to methods of using themto combat fungi, especially fungal infections in plants, and to regulateplant growth.

The invention provides a compound having the general formula (I):##STR2## and stereoisomers thereof, wherein X is halogen (fluorine,chlorine, bromine or iodine), optionally substituted alkyl, optionallysubstituted cycloalkyl, optionally substituted aralkyl, optionallysubstituted aryloxyalkyl, optionally substituted alkenyl, optionallysubstituted alkynyl, optionally substituted aryl, optionally substitutedamino, optionally substituted arylazo, optionally substitutedheteroarylalkyl, optionally substituted heteroaryloxyalkyl, optionallysubstituted acylamino, nitro, nitrile, --OR¹, --SR¹, --CO₂ R², --CONR³R⁴, --COR⁵, --CR⁶ ═NR⁷, --N═CR⁸ R⁹, --COR¹⁰ or --SO₂ R¹¹ ; W, Y and Z,which may be the same or different, are any of the atoms or groupslisted for X above and, in addition, may be hydrogen atoms; or any twoof the groups W, X, Y and Z, in adjacent positions on the phenyl ring,optionally join to form a fused ring, either aromatic or aliphatic,optionally containing one or more heteroatoms; R¹ is optionallysubstituted alkyl, or cycloalkyl optionally containing a hetero atom inthe cycloalkyl ring, optionally substituted alkenyl, optionallysubstituted acyl, optionally substituted aryl, optionally substitutedheteroaryl, optionally substituted aralkyl, or optionally substitutedheteroarylalkyl; R², R³, R⁴, R⁵, R⁶, R⁸, R⁹, R¹⁰ and R¹¹, which may bethe same or different, are hydrogen or optionally substituted alkyl,cycloalkyl, cycloalkylalkyl, optionally substituted alkenyl, optionallysubstituted aralkyl, optionally substituted aryl or optionallysubstituted heteroaryl; and R⁷ is optionally substituted aryl.

Of particular interest are those compounds of formula (I) in which X isoptionally substituted aralkyl, optionally substituted heteroarylalkyl,optionally substituted aryloxyalkyl, optionally substitutedheteroaryloxyalkyl, optionally substituted alkenyl (especiallyoptionally substituted aryl- or optionally substitutedheteroaryl-ethenyl), optionally substituted alkynyl (especiallyoptionally substituted aryl- or optionally substitutedheteroaryl-ethynyl), optionally substituted acylamino (especiallyoptionally substituted aryl- or optionally substitutedheteroaryl-carbonylamino), --OR¹, --SR¹ or --CO₂ R² ; W, Y and Z, whichare the same or different, are single atoms or sterically small groupssuch as fluoro, chloro, bromo, hydroxy, methyl, methoxy,trifluoromethyl, methylamino or dimethylamino but are preferablyhydrogen; or W and X, when in adjacent positions on the phenyl ring,join to form a fused ring, either aromatic or aliphatic, optionallycontaining one or more heteroatoms; R¹ is optionally substituted aryl,optionally substituted heteroaryl, optionally substituted aralkyl oroptionally substituted heteroarylalkyl and R² is optionally substitutedalkyl (especially C₁₋₄ alkyl) or optionally substituted aryl.

The compounds of the invention contain at least one carbon-nitrogendouble bond, and are sometimes obtained in the form of mixtures ofgeometric isomers. However, these mixtures can be separated intoindividual isomers, and this invention embraces such isomers, andmixtures thereof in all proportions including those which consistsubstantially of the (E)-isomer and those which consist substantially ofthe (Z)-isomer.

The individual stereoisomers which result from the unsymmetricallysubstituted double bond of the oxime ether group are identified by thecommonly used terms "(E)" and "(Z)". These terms are defined accordingto the Cahn-Ingold-Prelog system which is fully described in theliterature (see, for example, J. March, "Advanced Organic Chemistry" 3rdedition, Wiley-Interscience, Page 109 et seq).

The use hereinafter of the formula: ##STR3## signifies a separablemixture of both geometric isomers about the carbon-nitrogen double bondof the oxime ether, i.e. ##STR4##

Geometric pairs of isomers of the compounds listed later in Table I areidentified by the letters A and B. In many instances, using solventsystems such as ether or ethyl acetate, or mixtures of one of these withpetrol, the isomers A and B of a compound have significantly differentR_(f) values when analysed by thin-layer chromatography on silica gel.Of each pair of isomers the isomer which is the less polar on silica gelis terms Isomer A and the more polar one, Isomer B. In the case of thetwo geometric isomers of methyl O-methyl(2-phenoxyphenyl)oximino-acetate(compounds numbers 5 and 6 of Table I), Isomer B has been shownunambiguously by X-ray analysis to be the (E)-isomer. It is believedthat for every isomer pair, Isomer B corresponds to the (E)-isomer andIsomer A corresponds to the (Z)-isomer but this has not been proven.Generally the B isomers are the more active ones fungicidally and form apreferred embodiment of the invention.

In the compounds of formula (I), alkyl groups and alkyl moieties in, forexample, "alkoxy", "alkylthio", "aralkyl" and "heteroaryloxyalkyl"groups can be in the form of straight or branched chains and preferablycontain 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms.Examples are methyl, ethyl, propyl (n-and iso-propyl) and butyl (n-,sec-, iso- and tert-butyl). Optional substituents of alkyl includehydroxy, halogen (especially chlorine or fluorine), and alkoxycarbonyl.Trifluoromethyl is a particular example of optionally substituted alkyl.Cycloalkyl is preferably C₃₋₆ cycloalkyl and includes cyclohexyl. Anexample of a cycloalkyl group containing a hetero-atom istetrahydropyranyl. Cycloalkylalkyl is preferably C₃₋₆cycloalkyl(C₁₋₄)alkyl, for example, cyclopropylethyl.

Aralkyl includes, particularly, phenylalkyl (especially benzyl,phenylethyl, phenylpropyl, phenylbutyl or phenylhexyl) in which thealkyl moiety may carry other substituents such as hydroxy or C₁₋₄ alkoxyand the aryl moiety may be substituted with, for example, one or more ofhalogen (especially chlorine or fluorine), hydroxy, C₁₋₄ alkyl(especially methyl), C₁₋₄ alkoxy (especially methoxy), trifluoromethyl,trifluoromethoxy, optionally substituted phenoxy, optionally substitutedbenzyloxy, nitro, amino, phenyl, carboxy or a carboxylic acid ester,cyano, alkylcarbonylamino and methylenedioxy. Substituents which may bepresent on the phenoxy and benzyloxy groups include any of these othersubstituents which may be present on the aryl moiety of aralkyl.

Aryloxyalkyl includes, in particular, phenoxyalkyl (especiallyphenoxymethyl and phenoxyethyl) in which the alkyl moiety may carryother substituents such as methoxy and the aryl moiety may besubstituted in the same way as the aryl moiety in aralkyl above.

Alkenyl and alkynyl groups preferably contain 2 to 6 carbon atoms and,more preferably, 2 to 4 carbon atoms in the form of straight or branchedchains. Ethenyl, propenyl and butenyl are examples of alkenyl groups.Optional substituents of alkenyl include aromatic and heteroaromaticgroups (such as phenyl, furyl, thienyl and pyridyl) which may themselvescarry substituents such as those described for the aryl moiety ofaralkyl above. These include halogen (especially chlorine or fluorine).Further, the terminal carbon atoms of the alkenyl groups may form partof a 5- or 6-membered cycloalkyl group. Alkynyl includes ethynyl and isoptionally substituted by, for example, phenyl which may itself besubstituted as for the aryl moiety of aralkyl above.

Aryl is preferably phenyl. It may be substituted in the same way as thearyl moiety of aralkyl above.

Optional substituents which may be carried by an amino group include oneor two of N-aryl and N-alkyl groups (such as N-phenyl or N-methyl).

Arylazo is, for example, phenylazo in which the aryl moiety isoptionally substituted by, for example, alkynyl, alkoxy (especiallymethoxy) or dialkylamino (especially dimethylamino).

Heteroaryl wherever it appears (as a substituent on its own or as partof another substituent such as "heteroaryloxy-alkyl") includes 5- and6-membered heteroaromatic ring systems which may be fused with one ormore other aromatic or heteroaromatic rings. Examples are pyridyl,pyrimidinyl, pyrazinyl, pyridazinyl, furyl, thienyl, pyrrolyl,thiazolyl, benzoxazolyl and benzthiazolyl. Optional substituents includethose described for the aryl moiety of aralkyl above.

Acyl includes, in particular, acetyl and benzoyl, and acylamino includesbenzoylamino, furoylamino and thienylcarbonylamino optionallysubstituted by, for example, N-alkyl (especially N-methyl).

In one particular aspect, the invention includes compounds of formula(I) in which X is a group Ar-A- wherein A is a linking group such as O,S, CHR'--CHR", CH═CH, C═C, OCHR', CHR'O, O₂ C or CONR', R' and R" areindependently methyl or, preferably, hydrogen and Ar is aryl (forexample phenyl or naphthyl), heteroaryl (for example furyl, thienyl,pyridyl, pyrimidinyl or pyrazinyl) or cyclohexyl, the aryl andheteroaryl moieties being optionally substituted with, for example, oneor more of halo (especially fluoro or chloro), methyl, methoxy or nitro;and W, Y and Z are preferably hydrogen or one or more are single atomssuch as fluorine or chlorine or sterically small groups such as methylor methoxy, or when W is in an adjacent position to X on the phenylring, Ar is phenyl and A is O or S, W joins Ar at the carbon atomadjacent to that attached to A, optionally via a linking oxygen orsulphur atom, to form a fused ring.

Preferably A is 0 or CH═CH and Ar is furyl or phenyl optionallysubstituted with fluoro, chloro, methoxy or nitro and W, Y and Z arehydrogen.

The invention is illustrated by the compounds listed in Table I whichfollows.

                                      TABLE I                                     __________________________________________________________________________     ##STR5##                              (I)                                                                 MELTING                                          COMPOUND                     POINT                                            NO      X           W  Y  Z  (°C.)                                                                        ISOMER*                                    __________________________________________________________________________     1      ( .sub.--E)-C.sub.6 H.sub.5 CH:CH                                                         H  H  H  Oil   A                                           2      ( .sub.--E)-C.sub.6 H.sub.5 CH:CH                                                         H  H  H  77-78 B                                           3      ( .sub.--E)-2-C.sub.4 H.sub.3 O.CH:CH                                                     H  H  H  Oil   A                                           4      ( .sub.--E)-2-C.sub.4 H.sub.3 O.CH:CH                                                     H  H  H  87-88 B                                           5      C.sub.6 H.sub.5 O                                                                         H  H  H  Oil   A                                           6      C.sub.6 H.sub.5 O                                                                         H  H  H  108-111                                                                             B                                           7      4-NO.sub.2 C.sub.6 H.sub.4 O                                                              H  H  H    99-99.5                                                                           .sup. B.sup.+                               8      2,4-di-NO.sub.2C.sub.6 H.sub.3 O                                                          H  H  H  Oil   A                                           9      2,4-di-NO.sub.2C.sub.6 H.sub.3 O                                                          H  H  H  131-133                                                                             B                                          10      C.sub.6 H.sub.11 O                                                                        H  H  H  Oil   A                                          11      C.sub.6 H.sub.11 O                                                                        H  H  H  Oil   B                                          12      C.sub.6 H.sub.5 CONH                                                                      H  H  H  153   .sup. B.sup.+                              13      2-C.sub.4 H.sub.3 O.CONH                                                                  H  H  H   98   A                                          14      2-C.sub.4 H.sub.3 O.CONH                                                                  H  H  H  138-139                                                                             B                                          15      2-C.sub.4 H.sub.3 S.CONH                                                                  H  H  H  103   A                                          16      2-C.sub.4 H.sub.3 S.CONH                                                                  H  H  H  139-140                                                                             B                                          17      ⊕       ⊕                                                                            H  H  Oil   A                                          18      ⊕       ⊕                                                                            H  H  119-120                                                                             B                                          19      C.sub.6 H.sub.5 O                                                                         5-F                                                                              H  H        A                                          20      C.sub.6 H.sub.5 O                                                                         5-F                                                                              H  H        B                                          21      3-FC.sub.6 H.sub.4 O                                                                      H  H  H        A                                          22      3-FC.sub.6 H.sub.4 O                                                                      H  H  H        B                                          23      4-FC.sub.6 H.sub.4 O                                                                      H  H  H        A                                          24      4-FC.sub.6 H.sub.4 O                                                                      H  H  H        B                                          25      3-ClC.sub.6 H.sub.4 O                                                                     H  H  H        A                                          26      3-ClC.sub.6 H.sub.4 O                                                                     H  H  H        B                                          27      4-MeOC.sub.6 H.sub.4 O                                                                    H  H  H        A                                          28      4-MeOC.sub.6 H.sub.4 O                                                                    H  H  H        B                                          29      C.sub.6 H.sub.5 CH.sub.2 CH.sub.2                                                         H  H  H        A                                          30      C.sub.6 H.sub.5 CH.sub.2 CH.sub.2                                                         H  H  H        B                                          31      ⊕       ⊕                                                                            H  H  Oil   A                                          32      ⊕       ⊕                                                                            H  H  Oil   B                                          33      2-C.sub.4 H.sub.3 S.CON(CH.sub.3)                                                         H  H  H  166   .sup. B.sup.+                              34      C.sub.6 H.sub.5.OCH.sub.2                                                                 H  H  H        A                                          35      C.sub.6 H.sub.5.OCH.sub.2                                                                 H  H  H        B                                          36      2-CH.sub.3C.sub.6 H.sub.4.OCH.sub.2                                                       H  H  H        A                                          37      2-CH.sub.3C.sub.6 H.sub.4.OCH.sub.2                                                       H  H  H        B                                          38      3-ClC.sub.6 H.sub.4.OCH.sub.2                                                             H  H  H        A                                          39      3-ClC.sub.6 H.sub.4.OCH.sub.2                                                             H  H  H  53-54 .sup. B.sup.+                              40      4-CH.sub.3 OC.sub.6 H.sub.4.OCH.sub.2                                                     H  H  H        A                                          41      4-CH.sub.3 OC.sub.6 H.sub.4.OCH.sub.2                                                     H  H  H        B                                          42      3-ClC.sub.6 H.sub.4.OCH(CH.sub.3)                                                         H  H  H        A                                          43      3-ClC.sub.6 H.sub.4.OCH(CH.sub.3)                                                         H  H  H        B                                          44      CH.sub.3    H  H  H        A                                          45      CH.sub.3    H  H  H  64-65 .sup. B.sup.+                              46      BrCH.sub.2  H  H  H        A                                          47      BrCH.sub.2  H  H  H        B                                          48      (CH.sub.3 CH.sub.2 O).sub.2 P(O)CH.sub.2                                                  H  H  H        A                                          49      (CH.sub.3 CH.sub.2 O).sub.2 P(O)CH.sub.2                                                  H  H  H        B                                          50      ( .sub.--E)-4-FC.sub.6 H.sub.4.CH:CH                                                      H  H  H        A                                          51      ( .sub.--E)-4-FC.sub.6 H.sub.4.CH:CH                                                      H  H  H        B                                          52      C.sub.6 H.sub.5 CH.sub.2 O                                                                H  H  H        A                                          53      C.sub.6 H.sub.5 CH.sub.2 O                                                                H  H  H        B                                          54      3,5-di-ClC.sub.6 H.sub. 3 CH.sub.2 O                                                      H  H  H        A                                          55      3,5-di-ClC.sub.6 H.sub.3 CH.sub.2 O                                                       H  H  H        B                                          56      C.sub.6 H.sub.5.OCH.sub.2                                                                 3-F                                                                              5-F                                                                              6-F      A                                          57      C.sub.6 H.sub.5.OCH.sub.2                                                                 3-F                                                                              5-F                                                                              6-F      B                                          58                                                                                     ##STR6##   H  H  H        A                                          59                                                                                     ##STR7##   H  H  H        B                                          60                                                                                     ##STR8##   H  H  H        A                                          61                                                                                     ##STR9##   H  H  H        B                                          62                                                                                     ##STR10##  H  H  H        A                                          63                                                                                     ##STR11##  H  H  H        B                                          64                                                                                     ##STR12##  H  H  H        A                                          65                                                                                     ##STR13##  H  H  H        B                                          66      C.sub.6 H.sub.5.S                                                                         H  H  H        A                                          67      C.sub.6 H.sub.5.S                                                                         H  H  H        B                                          68      C.sub.6 H.sub.5.C...C                                                                     H  H  H        A                                          69      C.sub.6 H.sub.5.C...C                                                                     H  H  H        B                                          70      C.sub.6 H.sub.5.O.sub.2 C                                                                 H  H  H        A                                          71      C.sub.6 H.sub.5.O.sub.2 C                                                                 H  H  H        B                                          72      CH.sub.3 O.sub.2 C                                                                        H  H  H        A                                          73      CH.sub.3 O.sub.2 C                                                                        H  H  H  138   .sup. B.sup.+                              __________________________________________________________________________     *This refers to the geometry about the carbonnitrogen double bond. Isomer     A is the less polar of the 2 isomers on silica gel.                           C.sub.6 H.sub.5 is a phenyl group.                                            C.sub.6 H.sub.11 O is a cyclohexyloxy group.                                  C.sub.4 H.sub.3 O is a furyl group.                                           C.sub.4 H.sub.3 S is a thienyl group.                                         ⊕ Substituents join to form a fused ring. Thus compounds 17 and 18 ar     isomers of                                                                    ##STR14##                                                                     -                                                                             and compounds 31 and 32 are isomers of                                        ##STR15##                                                                     -                                                                             .sup.+ Single stereoisomer prepared. It is therefore uncertain whether        this is isomer A or B. For compound number 45, see comments in Example 3.

                  TABLE II                                                        ______________________________________                                        SELECTED PROTON NMR DATA                                                      COMPOUND                                                                      NO             DATA                                                           ______________________________________                                         1             3.78(3H, s); 4.03(3H, s); 7.01                                                (1H, d -J16Hz); 7.24-7.56                                                     (9H, m); 7.68(1H, d -J8Hz)ppm                                   2             3.82(3H, s); 4.03(3H, s); 6.87                                                (1H, d -J16Hz); 7.06(1H, d -J                                                 16Hz); 7.14-7.48(8H, m); 7.74                                                 (1H, d -J8Hz)ppm.                                               3             3.83(3H, s); 4.07(3H, s)ppm.                                    4             3.86(3H, s); 4.06(3H, s); 6.35                                                and 6.42(each 1H, apparently d                                                 -J5Hz); 6.79 and 6.86(each 1H,                                               d -J16Hz); 7.66(1H, d -J8Hz)                                                  ppm.                                                            5             3.63(3H, s); 4.01(3H, s)ppm.                                    6             3.76(3H, s); 4.00(3H, s)ppm.                                    7             3.78(3H, s); 3.96(3H, s); 7.0-                                                7.1(3H, m); 7.3-7.5(3H, m); 8.21                                              (2H, d -J8Hz)ppm.                                               8             3.77(3H, s); 3.94(3H, s); 6.86                                                (1H, d -J10Hz); 7.13(1H, d -J                                                 8Hz); 7.42(1H, m); 7.56(1H, m);                                               7.83(1H, dd -J8 and 1Hz), 8.30                                                (1H, dd -J8 and 2Hz); 8.89(1H,                                                d -J2Hz)ppm.                                                    9             3.84(3H, s); 3.99(3H, s), 7.06                                                (1H, d -J10Hz); 7.16(1H, d -J                                                 8Hz); 7.42(2H, m), 7.55(1H, m);                                               8.29(1H, dd -J10 and 2Hz); 8.82                                               (1H, d -J2Hz)ppm.                                              10             3.80(3H, s); 3.96(3H, s); 4.2                                                 (1H, brs); 6.60-7.60(4H, m)ppm.                                11             3.80(3H, s); 3.96(3H, s); 4.2                                                 (1H, brs); 6.75-7.20(4H, m)ppm.                                12             3.78(3H, s); 4.03(3H, s); 7.1-                                                8.3(10H, m)ppm.                                                13             3.90(3H, s); 4.11(3H, s); 6.48                                                (1H, dd -J4 and 2Hz); 7.0-7.5                                                 (5H, m); 8.81(1H, d -J8Hz); 9.8                                               (1H, brs)ppm.                                                  14             3.81(3H, s); 4.11(3H, s); 6.48                                                (1H, dd -J4 and 2Hz); 7.1-7.5                                                 (5H, m); 8.10(1H, d -J9Hz); 8.3                                               (1H, brs)ppm.                                                  15             4.00(3H, s); 4.12(3H, s), 7.0-                                                7.8(6H, m); 8.80(1H, d -J8Hz),                                                11.1(1H, s)ppm.                                                16             3.88(3H, s); 4.18(3H, s), 7.0-                                                7.3(6H, m); 8.05(1H, d -J8Hz);                                                8.1(1H, s)ppm.                                                 17             4.02(3H, s); 4.11(3H, s); 7.3-                                                7.4(2H, m); 7.42-7.56(2H, m);                                                 7.81(1H, d -J8Hz); 7.9-8.02                                                   (2H, m)ppm.                                                    18             3.91(3H, s); 4.10(3H, s); 7.32-                                               7.52(4H, m); 7.54(1H, d -J8Hz);                                               7.92-8.06(2H, m)ppm.                                           31             3.92(3H, s); 4.04(3H, s); 6.72-                                               6.96(6H, m); 7.25-7.35(1H, m)                                                 ppm.                                                           32             3.87(3H, s); 4.08(3H, s); 6.74-                                               6.98(7H, m)ppm.                                                33             3.3(3H, s); 3.7(3H, s); 3.82                                                  (3H, s); 6.56-7.62(7H, m)ppm.                                  ______________________________________                                         Table II shows selected proton NMR data for certain compounds described i     Table I. Chemical shifts are measured in ppm from tetramethylsilane, and      deuterochloroform was used as solvent throughout. The following               abbreviations are used:                                                       br = broad                                                                    t = triplet                                                                   s = singlet                                                                   q = quartet                                                                   d = doublet                                                                   m = multiplet                                                                 -J = coupling constant                                                        Hz = Hertz                                                               

The compounds of the invention having the general formula (I) can beprepared by the routes shown in Scheme I. Throughout Scheme I the termsW, X, Y and Z are as defined above, L is a halogen atom (a bromine,iodine or chlorine atom), and M is a metal atom (such as a lithium atom)or a metal atom plus an associated halogen atom (such as MgI, MgBr orMgCl). ##STR16##

Thus compounds of the invention having the general formula (I) can beprepared by treating ketoesters of general formula (II) withmethoxylamine (or a salt of methoxylamine) in a suitable solvent and ata suitable temperature.

Alternatively, compounds of the invention having the general formula (I)can be prepared by methylation of oximes of general formula (III) usinga methylating agent such as a methyl halide (methyl iodide, methylbromide or methyl chloride) or dimethyl sulphate, usually in thepresence of a base such as sodium methoxide, in a suitable solvent andat a suitable temperature (see, for example, H. S. Anker and H. T.Clarke, Organic Syntheses, Collective Vol. 3, 172). Diazomethane mayalso be used for this O-methylation.

Oximes of general formula (III) can be prepared by treatment ofketoesters of general formula (II) with hydroxylamine (or a salt ofhydroxylamine) in a suitable solvent and at a suitable temperature.

Alternatively, oximes of general formula (III) can be prepared bynitrosation of phenylacetates of general formula (IV) using nitrous acidor an ester of nitrous acid, usually in the presence of a base such assodium methoxide, in a suitable solvent and at a suitable temperature(see, for example, O. Touster, Organic Reactions, 1953, 7, 327,particularly page 342 and S. Kukolja, S. E. Draheim, B. J. Graves, D. C.Hunden, J. L. Pfeil, R. D. G. Copper, J. L. Ott, and F. T. Counter, J.Med. Chem., 1985, 28, 1896).

Other methods for the preparation of oximes (III) have been reported inthe chemical literature (see, for example, T. Shimizu, Y. Hayashi and K.Teramura, Bull. Chem. Soc. Jpn., 1985, 58, 2519; G. W. Shaffer, Can. J.Chem., 1970, 48, 1948).

Ketoesters of general formula (II) can be prepared by the followingmethods. Each transformation is often performed in a convenient solvent.

(i) By treatment of metallated species of general formula (VI) withdimethyl oxalate (see for example, EP-A-0178826).

(II) By Friedel-Crafts acylation of substituted benzenes (VII) usingmethyl oxalyl chloride in the presence of an acid, especially a Lewisacid, in catalytic or stoichiometric amounts.

(III) By oxidation of phenylacetates of general formula (IV) using, forexample, selenium dioxide.

Halobenzenes of general formula (V), benzenes of general formula (VII),and phenylacetates of general formula (IV) can be made by standardprocedures described in the chemical literature.

In all of the methods described above, the function CH₃ O₂ C.C:N.OCH₃ isconstructed from precursors in which the groups W, X, Y and Z arealready intact. It is also possible to construct the function CH₃ O₂C.C:N.OCH₃ and then to modify the groups W, X, Y and Z. For example, ina compound (I) wherein X is a methyl group, it is possible to convertthis methyl group first into a bromomethyl group by treatment withN-bromosuccinimide, then into a phosphonomethyl group by treatment witha trialkyl phosphite, and then into a styryl group by treatment with abase and then benzaldehyde (cf. EP-A-0203606). When such a method isused to make compounds in which W, Y and Z are all hydrogen, Compounds44 to 49 of Table I are key intermediates.

In further aspects the invention provides processes as herein describedfor preparing the compounds of formula (I). It also provides theintermediate chemical of formula (III) and, as intermediate chemicals,Compounds 44 to 49 of Table I.

The compounds of the invention are active fungicides, and may be used tocontrol one or more of the following pathogens:

Pyricularia oryzae on rice.

Puccinia recondita, Puccinia striiformis and other rusts on wheat,Puccinia hordei, Puccinia striiformis and other rusts on barley, andrusts on other hosts e.g. coffee, pears, apples, peanuts, vegetables andornamental plants. Erysiphe graminis (powdery mildew) on barley andwheat and other powdery mildews on various hosts such as Sphaerothecamacularis on hops, Sphaerotheca fuliginea on cucurbits (e.g. cucumber),Podosphaera leucotricha on apples and Uncinula necator on vines.

Helminthosporium spp., Rhynchosporium spp., Septoria spp., andPseudocercosporella herpotrichoides on cereals. Cercospora arachidicolaand Cercosporidium personata on peanuts and other Cercospora species onother hosts for example sugar beet, bananas, soya beans and rice.

Venturia inaequalis (scab) on apples.

Plasmopara viticola on vines.

Other downy mildews such as Bremia lactucae on lettuce, Peronospora spp.on soybeans, tobacco, onions and other hosts and Pseudoperonosporahumuli on hops and Pseudoperonospora cubensis on cucurbits.

Phytophthora infestans on potatoes and tomatoes and other Phytophthoraspp. on vegetables, strawberries, avocado, pepper, ornamentals, tobacco,cocoa and other hosts.

Some of the compounds have also shown a broad range of activitiesagainst fungi in vitro.

Some of the compounds may also have activity against variouspost-harvest pathogens of fruit (e.g. Penicillium digitatum and italicumand Trichoderma viride on oranges, Gloeosporium musarum on bananas andBotrytis cinerea on grape).

The compounds may also be useful as industrial (as opposed toagricultural) fungicides, e.g. in the prevention of fungal attack onwood, hides, leather and especially paint films.

The compounds may move locally in plant tissue. Moreover, the compoundsmay be volatile enough to be active in the vapour-phase against fungi onthe plant.

Therefore in another aspect the invention provides a method of combatingfungi, which comprises applying to a plant, to a seed of a plant, or tothe locus of the plant or seed, a fungicidally effective amount of acompound of formula (I) as hereinbefore defined, or a compositioncontaining the same.

Some compounds exhibit plant growth regulating activity and may bedeployed for this purposes, again at appropriate rates of application.

Therefore, in yet another aspect the invention provides a method ofregulating plant growth which comprises applying to a plant an effectiveamount of a plant growth regulating compound of formula (I).

The compounds may be used directly for agricultural purposes but aremore conveniently formulated into compositions using a carrier ordiluent. The invention thus provides a fungicidal or plant growthregulator composition comprising an effective amount of a compound offormula (I) as hereinbefore defined, and an acceptable carrier ordiluent therefor.

The compounds, can be applied in a number of ways. For example they canbe applied, formulated or unformulated, directly to the foliage of aplant, to seeds or to other medium in which plants are growing or are tobe planted. They can be sprayed on, dusted on or applied as a cream orpaste formulation; or they can be applied as a vapour or as slow releasegranules. Application can be to any part of the plant including thefoliage, stems, branches or roots, or to soil surrounding the roots, orto the seed before it is planted; or to the soil generally, to paddywater or to hydroponic culture systems. The invention compounds may alsobe injected into plants or sprayed onto vegetation using electrodynamicspraying techniques or other low volume methods.

The term "plant" as used herein includes seedlings, bushes and trees.Furthermore, the fungicidal method of the invention includespreventative, protectant, prophylactic and eradicant treatment.

The compounds are preferably used for agricultural and horticulturalpurposes in the form of a composition. The type of composition used inany instance will depend upon the particular purpose envisaged.

The compositions may be in the form of dustable powders or granulescomprising the active ingredient (invention compound) and a soliddiluent or carrier, for example fillers such as kaolin, bentonite,kieselguhr, dolomite, calcium carbonate, talc, powdered magnesia,Fuller's earth, gypsum, diatomaceous earth and China clay. Such granulescan be preformed granules suitable for application to the soil withoutfurther treatment. These granules can be made either by impregnatingpellets of filler with the active ingredient or by pelleting a mixtureof the active ingredient and powdered filler. Compositions for dressingseed may include an agent (for example a mineral oil) for assisting theadhesion of the composition to the seed; alternatively the activeingredient can be formulated for seed dressing purposes using an organicsolvent (for example N-methylpyrrolidone, propylene glycol ordimethylformamide). The compositions may also be in the form of wettablepowders or water dispersible granules comprising wetting or dispersingagents to facilitate their dispersion in liquids. The powders andgranules may also contain fillers and suspending agents.

Emulsifiable concentrates or emulsions may be prepared by dissolving theactive ingredient in an organic solvent optionally containing a wettingor emulsifying agent and then adding the mixture to water which may alsocontain a setting or emulsifying agent. Suitable organic solvents arearomatic solvents such as alkylbenzenes and alkylnaphthalenes, ketonessuch as isophorone, cyclohexanone and methylcyclohexanone, chlorinatedhydrocarbons such as chlorobenzene and trichlorethane, and alcohols suchas benzyl alcohol, furfuryl alcohol, butanol and glycol ethers.

Suspension concentrates of largely insoluble solids may be prepared byball or bead milling with a dispersing agent and including a suspendingagent to stop the solid settling.

Compositions to be used as sprays may be in the form of aerosols whereinthe formulation is held in a container under pressure in the presence ofa propellant, e.g. fluorotrichloromethane or dichlorodifluoromethane.

The invention compounds can be mixed in the dry state with a pyrotechnicmixture to form a composition suitable for generating in enclosed spacesa smoke containing the compounds.

Alternatively, the compounds may be used in a micro-encapsulated form.They may also be formulated in biodegradable polymeric formulations toobtain a slow, controlled release of the active substance.

By including suitable additives, for example additives for improving thedistribution, adhesive power and resistance to rain on treated surfaces,the different compositions can be better adapted for various utilities.

The inclusion of a photostabiliser may enhance the persistence of thecompounds in their biological effect. Suitable stabilisers may includethe commercially available benzotriazole stabilisers, such as2-(2'-hydroxy-5'-methylphenyl)benzotriazole, and benzophenonestabilisers, such as 2-hydroxy-4-methoxybenzophenone.

The invention compounds can be used as mixtures with fertilisers (e.g.nitrogen-, potassium- or phosphorus-containing fertilisers).Compositions comprising only granules of fertiliser incorporating, forexample coated with, the compound are preferred. Such granules suitablycontain up to 25% by weight of the compound. The invention thereforealso provides a fertiliser composition comprising a fertiliser and thecompound of general formula (I) or a salt or metal complex thereof.

Wettable powders, emulsifiable concentrates and suspension concentrateswill normally contain surfactants e.g. a wetting agent, dispersingagent, emulsifying agent or suspending agent. These agents can becationic, anionic or non-ionic agents.

Suitable cationic agents are quaternary ammonium compounds, for examplecetyltrimethylammonium bromide. Suitable anionic agents are soaps, saltsof aliphatic monoesters of sulphur acid (for example sodium laurylsulphate), and salts of sulphonated aromatic compounds (for examplesodium dodecylbenzenesulphonate, sodium, calcium or ammoniumlignosulphonate, butylnaphthalene sulphonate, and a mixture of sodiumdiisopropyl- and triisopropylnaphthalene sulphonates).

Suitable non-ionic agents are the condensation products of ethyleneoxide with fatty alcohols such as oleyl or cetyl alcohol, or with alkylphenols such as octyl- or nonyl-phenol and octylcresol. Other non-ionicagents are the partial esters derived from long chain fatty acids andhexitol anhydrides, the condensation products of the said partial esterswith ethylene oxide, and the lecithins. Suitable suspending agents arehydrophilic colloids (for example polyvinylpyrrolidone and sodiumcarboxymethylcellulose), and swelling clays such as bentonite orattapulgite.

Compositions for use as aqueous dispersions or emulsions are generallysupplied in the form of a concentrate containing a high proportion ofthe active ingredient, the concentrate being diluted with water beforeuse. These concentrates should preferably be able to withstand storagefor prolonged periods and after such storage be capable of dilution withwater in order to form aqueous preparations which remain homogeneous fora sufficient time to enable them to be applied by conventional sprayequipment. The concentrates may conveniently contain up to 95%, suitably10-85%, for example 25-60%, by weight of the active ingredient. Afterdilution to form aqueous preparations, such preparations may containvarying amounts of the active ingredient depending upon the intendedpurpose, but an aqueous preparation containing 0.0005% or 0.01% to 10%by weight of active ingredient may be used.

The compositions of this invention may contain other compounds havingbiological activity, e.g. compounds having similar or complementaryfungicidal activity or which possess plant growth regulating, herbicidalor insecticidal activity.

A fungicidal compound which may be present in the composition of theinvention may be one which is capable of combating ear diseases ofcereals (e.g. wheat) such as Septoria, Gibberella and Helminthosporiumspp., seed and soil borne diseases and downy and powdery mildews ongrapes and powdery mildew and scab on apple etc. By including anotherfungicide the composition can have a broader spectrum of activity thanthe compound of general formula (I) alone. Further the other fungicidecan have a synergistic effect on the fungicidal activity of the compoundof general formula (I). Examples of fungicidal compounds which may beincluded in the composition of the invention are carbendazim, benomyl,thiophanate-methyl, thiabendazole, fuberidazole, etridazole,dichlofluanid, cymoxanil, oxadixyl, ofurace, metalaxyl, furalaxyl,benalaxyl, fosetyl-aluminium, fenarimol, iprodione, prothiocarb,procymidone, vinclozolin, penconazole, myclobutanil, propamocarb,RO151297, diconazole, pyrazophos, ethirimol, ditalimfos, buthiobate,tridemorph, triforine, nuarimol, triazbutyl, guazatine, triacetate saltof 1,1'-iminodi-(octamethylene)diguanidine, propiconazole, prochloraz,4-chloro-N-(1-cyano-1-ethoxymethyl)benzamide, flutriafol, hexaconazole,(2RS,3RS)-2-(4-chlorophenyl)-3-cyclopropyl-1-(1H-1,2,4-triazol-1-yl)butan-2-ol,(RS)-1-(4-chlorophenyl)-4,4-dimethyl-3-(1H-1,2,4-triazol-1-ylmethyl)pentan-3-ol,DPX H6573 (1-((bis-4-fluorophenyl)methylsilyl)methyl)-1H-1,2,4-triazole,triadimefon, triadimenol, diclobutrazol, fenpropimorph, pyrifenox,fenpropidin, chlorozolinate, imazalil, fenfuram, carboxin, oxycarboxin,methfuroxam, dodemorph, BAS 454, blasticidin S, kasugamycin, edifenphos,Kitazin P, cycloheximide, phthalide, probenazole, isoprothiolane,tricyclazole, pyroquilon, chlorbenzthiazone, neoasozin, polyoxin D,validamycin A, mepronil, flutolanil, pencycuron, diclomezine, phenazinoxide, nickel dimethyldithiocarbamate, techlofthalam, bitertanol,bupirimate, etaconazole, hydroxyisoxazole, streptomycin, cyprofuram,biloxazol, quinomethionate, dimethirimol,1-(2-cyano-2-methoxyiminoacetyl)-3-ethyl urea, fenapanil,tolclofos-methyl, pyroxyfur, polyram, maneb, mancozeb, captafol,chlorothalonil, anilazine, thiram, captan, folpet, zineb, propineb,sulphur, dinocap, dichlone, chloroneb, binapacryl, nitrothal-isopropyl,dodine, dithianon, fentin hydroxide, fentin acetate, tecnazene,quintozene, dichloran, copper containing compounds such as copperoxychloride, copper sulphate and Bordeaux mixture, and organomercurycompounds.

The compounds of general formula (I) can be mixed with soil, peat orother rooting media for the protection of plants against seed-borne,soil-borne or foliar fungal diseases.

Suitable insecticides which may be incorporated in the composition ofthe invention include pirimicarb, dimethoate, demeton-s-methyl,formothion, carbaryl, isoprocarb, XMC, BPMC, carbofuran, carbosulfan,diazinon, fenthion, fenitrothion, phenthoate, chlorpyrifos, isoxathion,propaphos, monocrotophas, buprofezin, ethroproxyfen and cycloprothrin.

Plant growth regulating compounds are compounds which control weeds orseedhead formation, or selectively control the growth of less desirableplants (e.g. grasses).

Examples of suitable plant growth regulating compounds for use with theinvention compounds are the gibberellins (e.g. GA₃, GA₄ or GA₇), theauxins (e.g. indoleacetic acid, indolebutyric acid, naphthoxyacetic acidor naphthylacetic acid), the cytokinins (e.g. kinetin, diphenylurea,benzimidazole, benzyladenine or benzylaminopurine), phenoxyacetic acids(e.g. 2,4-D or MCPA), substituted benzoic acids (e.g. triiodobenzoicacid), morphactins (e.g. chlorfluoroecol), maleic hydrazide, glyphosate,glyphosine, long chain fatty alcohols and acids, dikegulac,paclobutrazol, flurprimidol, fluoridamid, mefluidide, substitutedquaternary ammonium and phosphonium compounds (e.g. chloromequatchlorphonium or mepiquatchloride), ethephon, carbetamide,methyl-3,6-dichloroanisate, daminozide, asulam, abscisic acid,isopyrimol,1-(4-chlorophenyl)-4,6-dimethyl-2-oxo-1,2-dihydropyridine-3-carboxylicacid, hydroxybenzonitriles (e.g. bromoxynil), difenzoquate,benzoylprop-ethyl 3,6-dichloropicolinic acid, fenpentezol, inabenfide,triapenthenol and tecnazene.

The following Examples illustrate the invention. Throughout theseExamples, the term "ether" refers to diethyl ether; magnesium sulphatewas used to dry solutions; nd reactions involving water-sensitiveintermediate were performed under nitrogen. Unless otherwise stated,chromatography was performed using silica gel as the stationary phase.Where shown, infrared and NMR data are selective; no attempt is made tolist every absorption. The following abbreviations are used throughout:

    ______________________________________                                        THF =  tetrahydrofuran                                                                              s =       singlet                                       DMF =   .sub.-- N, .sub.-- N-dimethyl-                                                              d =       doublet                                              formamide      t =       triplet                                       GC =   Gas chromatography                                                                           m =       multiplet                                     MS =   Mass spectrum  delta =   chemical shift                                mp =   Melting point  CDCl.sub.3 =                                                                            deutero-                                      ml =   milliliter(s)            chloroform                                    mg =   milligramme(s)  -J =     coupling constant                             g =    gramme(s)      Hz =      Hertz                                         ______________________________________                                    

EXAMPLE 1

This Example illustrates the preparation of the 2 geometric isomers ofmethyl O-methyl(2-phenoxyphenyl)oximino-acetate (compounds numbers 5 and6 of Table I).

n-Butyl-lithium (77 ml of a 2.6M solution in hexane) was added dropwiseover 30 minutes to a stirred solution of diphenyl ether (34.0 g) in dryether (300 ml), cooled to about 0° C. The resulting orange solution wasstirred at room temperature for 3 hours, allowed to stand overnight,then added dropwise over 1.5 hours to a stirred solution of dimethyloxalate (47.0 g) in dry THF (200 ml), cooled to just below 10° C. Theresulting mixture was allowed to stand overnight, and was then pouredinto water and extracted with ether. The extracts were washed withwater, dried and concentrated under reduced pressure to give a brown oil(58.57 g). Part of this oil (12.20 g) was purified by columnchromatography using 20% ether in petrol as eluant to give methylo-phenoxybenzoylformate (5.87 g, representing 55% yield) as a paleyellow oil.

A mixture of methyl o-phenoxybenzoylformate (2.56 g) and methoxylaminehydrochloride (1.25 g) in dry methanol (25 ml) was refluxed for about 3hours and allowed to cool. Most of the solvent was removed under reducedpressure and the residue was diluted with water and extracted withether. The extracts were washed with water, dried, concentrated underreduced pressure, and chromatographed using 20% ether in petrol to give(i) isomer A of the title compound, eluted first (0.55 g, 19% yield) asan oil; and (ii) isomer B of the title compound (1.68 g, 59% yield) as awhite solid, mp 108°-111° C. An X-ray crystal structure of isomer Bshowed that it is the (E)-isomer.

The following are examples of compositions suitable for agricultural andhorticultural purposes which can be formulated from the compounds of theinvention. Such compositions form another aspect of the invention.Temperatures are given in degrees centigrade (°C.), and percentages areby weight.

EXAMPLE 2

This Example illustrates the preparation of the 2 geometric isomers ofmethyl O-methyl (2-(E)-styrylphenyl)oximino-acetate (compounds numbers 1and 2 of Table I). ##STR17##

A mixture of the ketoester (A) (6.13 g, prepared by the method describedin EP-A-0178826, with a purity of 54% by GC, and containing the tertiaryalcohol (B) as the major impurity) and hydroxylamine hydrochloride (1.76g) in dry methanol (100 ml) was heated under reflux for 2.5 hours. Theresulting mixture was allowed to cool, and was poured into water andextracted with ether. The extracts were dried, concentrated andchromatographed using 30% ether in petrol as eluent to give (i) theoxime (C) (0.73 g, 21% yield) as an oil, eluted first and (ii) the oxime(D) (1.36 g, 39% yield), also an oil, eluted second.

A solution of the oxime (D) (1.36 g) in dry DMF (20 ml) was addeddropwise to a stirred suspension of sodium hydride (0.128 g) in dry DMF(50 ml). After 10 minutes, dimethyl sulphate (0.51 ml) was added to theresulting yellow solution and the colour was discharged. After a further30 minutes, the reaction mixture was poured into water and extractedwith ether. The extracts were washed with water (x2), dried andconcentrated to give a brown solid (1.44 g). This was combined with asimilar batch (0.17 g) from an earlier small-scale reaction, thenchromatographed to give isomer B of the tile compound (F) (1.12 g,representing a yield of 70%) as a white solid, mp. 77°-78° C., withproton NMR data as shown in Table II. The oxime (C) was convertedstereospecifically into isomer A of the title compound(E) (63% yield) byexactly the same method. Isomer A is an oil, with proton NMR data asshown in Table II.

EXAMPLE 3

This Example describes the preparation of a single stereoisomer ofmethyl O-methyl(2-methylphenyl)oximinoacetate (compound number 45 ofTable I).

Dry methanol (2.5 ml) was added dropwise to a stirred suspension ofsodium hydride (0.28 g) in dry ether (20 ml) to leave an almostcolourless solution. To this was added a mixture of methyl(2-methylphenyl)acetate (2.0 g) and n-butyl nitrite (1.38 g) in dryether (4 ml) to give, after an hour, a yellow suspension. After afurther hour, the reaction mixture was poured into water and washedtwice with ether. The resulting aqueous layer was diluted with aqueousammonium chloride (to give a white suspension) and then extracted withether (x3). These ether extracts were washed with water, dried andconcentrated to give a viscous oil (0.52 g) containing a singlestereoisomer of methyl (2-methylphenyl)oximino-acetate (70% by GC).Potassium carbonate (0.74 g) and, after 15 minutes, dimethyl sulphate(0.25 ml) were added to a stirred solution of this viscous oil in DMF(10 ml). After 2 hours, the reaction mixture was poured into water andextracted with ether. The combined extracts were washed with water,dried, concentrated and chromatographed using 20% ether in petrol aseluant to give the title compound (0.26 g, 10% yield from methyl(2-methylphenyl)acetate) as a white crystalline solid, mp. 64°-65° C.,infrared (nujol mull) 1728 cm⁻¹, NMR (CDCl₃): delta 2.20 (3H,s); 3.88(3H,s); 4.06 (3H,s) ppm.

Both stereoisomers of methyl O-methyl(phenyl)oximinoacetate wereprepared from methyl benzoylformate and methoxylamine hydrochloride bythe method described in Example 1. The single stereoisomer of the titlecompound whose preparation is described above had a very similar R_(f)-value on thin-layer chromatography to the more polar stereoisomer ofmethyl O-methyl(phenyl)oximino-acetate, and was markedly more polar thanthe less polar stereoisomer of methyl O-methyl(phenyl)oximino-acetate(silica gel; ether:petrol, 1:1).

EXAMPLE 4

This Example describes the preparation of a single stereoisomer ofmethyl O-methyl(2-(3-chlorophenoxymethyl)phenyl)oximino-acetate(compound number 39 of Table I).

A mixture of methyl O-methyl(2-methylphenyl)oximino-acetate (0.18 g, asingle stereoisomer prepared as described in Example 3),N-bromosuccinimide (0.154 g) and benzoyl peroxide (catalytic) in drycarbon tetrachloride (5 ml) was heated under reflux for 2 hours, allowedto cool, and filtered. The filtrate was concentrated under reducedpressure to give a pale yellow oil (0.25 g) containing a singlestereoisomer of methyl O-methyl(2-bromomethylphenyl)oximino-acetate (NMR(CDCl₃): delta 3.89 (3H,s); 4.07 (3H,s); 4.34 (2H,s) ppm). Solutions of3-chlorophenol (0.105 g) in dry DMF (1 ml) and, after 2 hours, this paleyellow oil in dry DMF (5 ml) were added to a stirred suspension ofsodium hydride (0.018 g) in dry DMF (10 ml). After 3 hours, the reactionmixture was poured into water and extracted with ether. The combinedextracts were washed successively with water, dilute aqueous sodiumhydroxide and aqueous sodium chloride, then dried, concentrated andchromatographed using 20% ether in petrol as eluant to give the titlecompound (0.17 g, 59% yield from methylO-methyl(2-methylphenyl)oximino-acetate) as a white solid, mp. 53°-54°C., infrared (nujol) 1729 cm⁻¹, NMR (CDCl₃): delta 3.85 (3H,s); 4.03(3H,s); 4.92 (2H,s) ppm.

EXAMPLE 5

An emulsifiable concentrate is made up by mixing and stirring theingredients until all are dissolved.

    ______________________________________                                        Compound No. 6 of Table I                                                                            10%                                                    Benzyl alcohol         30%                                                    Calcium dodecylbenzenesulphonate                                                                      5%                                                    Nonylphenolethoxylate (13 moles                                                                      10%                                                    ethylene oxide)                                                               Alkyl benzenes         45%                                                    ______________________________________                                    

EXAMPLE 6

The active ingredient is dissolved in methylene dichloride and theresultant liquid sprayed onto the granules of attapulgite clay. Thesolvent is then allowed to evaporate to produce a granular composition.

    ______________________________________                                        Compound No. 6 of Table I                                                                           5%                                                      Attapulgite granules 95%                                                      ______________________________________                                    

EXAMPLE 7

A composition suitable for use as a seed dressing is prepared bygrinding and mixing the three ingredients.

    ______________________________________                                        Compound No. 6 of Table I                                                                          50%                                                      Mineral oil           2%                                                      China clay           48%                                                      ______________________________________                                    

EXAMPLE 8

A dustable powder is prepared by grinding and mixing the activeingredient with talc.

    ______________________________________                                        Compound No. 6 of Table I                                                                           5%                                                      Talc                 95%                                                      ______________________________________                                    

EXAMPLE 9

A suspension concentrate is prepared by ball milling the ingredients toform an aqueous suspension of the ground mixture with water.

    ______________________________________                                        Compound No. 6 of Table I                                                                          40%                                                      Sodium lignosulphonate                                                                             10%                                                      Bentonite clay        1%                                                      Water                49%                                                      ______________________________________                                    

This formulation can be used as a spray by diluting with water orapplied directly to seed.

EXAMPLE 10

A wettable powder formulation is made by mixing together and grindingthe ingredients until all are thoroughly mixed.

    ______________________________________                                        Compound No. 6 of Table I                                                                          25%                                                      Sodium lauryl sulphate                                                                              2%                                                      Sodium lignosulphonate                                                                              5%                                                      Silica               25%                                                      China clay           43%                                                      ______________________________________                                    

EXAMPLE 11

The compounds were tested against a variety of foliar fungal diseases ofplants. The technique employed was as follows.

The plants were grown in John Innes Potting Compost (No 1 or 2) in 4 cmdiameter minipots. The test compounds were formulated either by beadmilling with aqueous Dispersol T or as a solution in acetone oracetone/ethanol which was diluted to the required concentrationimmediately before use. For the foliage diseases, the formulations (100ppm active ingredient) were sprayed on to the foliage and applied to theroots of the plants in the soil. The sprays were applied to maximumretention and the root drenches to a final concentration equivalent toapproximately 40 ppm a.i./dry soil. Tween 20, to give a finalconcentration of 0.05%, was added when the sprays were applied tocereals.

For most of the tests the compound was applied to the soil (roots) andto the foliage (by spraying) one or two days before the plant wasinoculated with the disease. An exception was the test on Erysiphegraminis in which the plants were inoculated 24 hours before treatment.Foliar pathogens were applied by spray as spore suspensions onto theleaves of test plants. After inoculation, the plants were put into anappropriate environment to allow infection to proceed and then incubateduntil the disease was ready for assessment. The period betweeninoculation and assessment varied from four to fourteen days accordingto the disease and environment.

The disease control was recorded by the following grading:

4=no disease

3-=trace-5% of disease on untreated plants

2=6-25% of disease on untreated plants

1=26-59% of disease on untreated plants

0=60-100% of disease on untreated plants

The results are shown in Table III.

                                      TABLE III                                   __________________________________________________________________________                 ERYSIPHE                                                         COM- PUCCINIA                                                                              GRAMINIS                                                                             VENTURIA                                                                              PYRICULARIA                                                                            CERCOSPORA                                                                              PLASMOPARA                     POUND                                                                              RECONDITA                                                                             HORDEI INAEQUALIS                                                                            ORYZAE   ARACHIDICOLA                                                                            VITICOLA                       NO.  (WHEAT) (BARLEY)                                                                             (APPLE) (RICE)   (PEANUT)  (VINE)                         __________________________________________________________________________    1    0       0      3       0        0         4                              2    2       0      4       0        0         4                              3    0       0      4       0        0         0                              4    4       0      4       3        3         4                              5    0       3      3       1        0         0                              6    4       4      4       3        3         4                              7    0       1      3       0        0         3                              10*  3       3      2       3        0         2                              13   0       0      --      0        2         0                              17   3       0      1       0        0         2                              18   3       0      4       1        1         4                              32   4       3      2       0        1         4                              33   0       0      4       0        0         0                              __________________________________________________________________________     *25 ppm foliar spray only                                                

EXAMPLE 12

This Example illustrates the plant growth regulating properties ofcompounds 1, 2, 5 and 12-15 of Table I when tested on a whole plantscreen against two species of plant. The plant species are identified inTable IV with the leaf stage at which they were sprayed.

A formulation of each chemical was applied at 4000 ppm (4 kg/ha in a1000 l/ha field volume) using a tracksprayer and a SS8004E (Teejet)nozzle.

After spraying, the plants were grown in a glasshouse with 25° C.day/22° C. night temperatures. Supplementary lighting was supplied whennecessary to provide an average photoperiod of 16 hours (14 hoursminimum).

After 2-6 weeks in the glasshouse, depending on species and time ofyear, the plants were visually assessed for morphologicalcharacteristics against a control plant sprayed with a blankformulation. The results are presented in Tables V and VI.

                  TABLE IV                                                        ______________________________________                                        PLANT MATERIAL USED FOR WHOLE PLANT SCREEN                                                          Growth Stage                                                                            No. Plants                                                                            Compost                               Species                                                                             Code   Variety  at Treatment                                                                            per 3" pot                                                                            Type                                  ______________________________________                                        Maize MZ     Earliking                                                                              21/4-21/2 leaves                                                                        1       PEAT                                  Apple AP     Red       4-5 leaves                                                                             1       JIP*                                               Delicious                                                        ______________________________________                                         *John Innes Potting compost                                              

                  TABLE V                                                         ______________________________________                                        MZ                                                                            Compound                                                                      No.        Table   R        G   A     I   P                                   ______________________________________                                        1          I       3        2   3     3   1                                   2          I       2            2     2                                       5          I       3            3     3   1                                   12         I       2                  1                                       13         I       2                  1                                       ______________________________________                                    

                  TABLE VI                                                        ______________________________________                                        AP                                                                            Compound                                                                      No.          Table   R          G   I                                         ______________________________________                                         2           I       2          1   1                                         12           I       2          1   1                                         13           I       2          1   1                                         14           I       1              1                                         15           I       1          1   1                                         ______________________________________                                    

KEY

R=Retardation

G=Greening effect

A=Apical damage

I=Interligular or internodal length reduction

P=Phytotoxicity

All effects except phytotoxicity, are scored visually on a 1-3 basiswhere

1=10-30%

2=31-60%

3=61-100%

Blank means less than 10% effect.

Phytotoxicity is scored on a 1-5 basis where

1=less than 10%

2=11-30%

3=31-50%

4=51-70%

5=greater than 70%

Blank means no effect at all observed.

We claim:
 1. A compound of the formula: ##STR18## where X is Cl or Br.2. A compound according to claim 1 wherein X is Br.